The photochemical nucleophile–olefin combination, aromatic substitution (photo-NOCAS) reaction (Part 4): methanol–olefins, methyl 4-cyanobenzoate

Abstract

Dicyanobenzene-1,4 (1) and -1,2 are known to undergo substitution upon irradiation, in the presence of an olefin, in acetonitrile–methanol (3:1) solution. The products are 1:1:1 (methanol:olefin:aromatic) adducts, substituted on the aromatic ring with loss of a cyano group. This reaction, referred to as the photo-NOCAS (nucleophile–olefin combination, aromatic substitution) reaction, has been shown to be fairly general with regard to the olefin and the nucleophile that can be incorporated. Less is known about the scope of the reaction incorporating other electron-withdrawing substituted aromatic molecules. The purpose of this study was to determine if methyl 4-cyanobenzoate (10) would also take part in this reaction, to form 4-substituted aromatic esters. Irradiation of acetonitrile–methanol solutions of 10 and olefins 2,3-dimethyl-2-butene (2) and 1-methylcyclohexene (5) gave cyclic imine esters, 11 and 13, respectively, instead of photo-NOCAS products. The photo-NOCAS products were obtained when the codonor biphenyl (4) was added to the irradiation mixture. Formation of the cyclic imine ester is attributed to excitation of the charge-transfer complex formed between 10 and the olefin. The addition of biphenyl (4) serves to generate the contact radical ion pair (CRIP) upon irradiation of the charge-transfer complex between 10 and 4. This CRIP can dissociate to the solvent-separated radical ions, the radical cation of 4 can accept an electron from the olefin, and the olefin radical cation can go on to give the photo-NOCAS products. Irradiation of a solution of 10 and 2 in nonpolar solvent (benzene) gave the oxetane, believed to arise from the exciplex. In addition to photo-NOCAS products from 10, 4-cyanophenylketones 17 and 23 are also formed by attack of the β-alkoxyalkyl radical at the carboxyl carbonyl. The differences in behaviour between 1,4-dicyanobenzene (1) and methyl 4-cyanobenzoate (10) under these reaction conditions are described and explained.